Methylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N-Alkylation

We elucidate the mechanism of the manganese-catalyzed N-alkylation of aniline with benzyl alcohol mediated by a bis(1,2,3-triazolylidene) Mn(I) complex through a combination of experimental studies and density functional theory (DFT) calculations. Activation of the precatalyst by a base leads to the...

Descripción completa

Detalles Bibliográficos
Autores: Batuecas, Maria, Garcia, Beatriz, Saviozzi, Chiara, Viana, Maria S., Maseras, Feliu, Royo, Beatriz
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2026
País:España
Institución:Universidad de Zaragoza
Repositorio:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:dnet:zaguan______::acda99d7d6f095bf2126ca01131c7de8
Acceso en línea:http://zaguan.unizar.es/record/171047
Access Level:acceso abierto
id ES_5bc1ddac04020a2880fafd23ddb4fbaf
oai_identifier_str oai:dnet:zaguan______::acda99d7d6f095bf2126ca01131c7de8
network_acronym_str ES
network_name_str España
repository_id_str
spelling Methylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N-AlkylationBatuecas, MariaGarcia, BeatrizSaviozzi, ChiaraViana, Maria S.Maseras, FeliuRoyo, BeatrizWe elucidate the mechanism of the manganese-catalyzed N-alkylation of aniline with benzyl alcohol mediated by a bis(1,2,3-triazolylidene) Mn(I) complex through a combination of experimental studies and density functional theory (DFT) calculations. Activation of the precatalyst by a base leads to the formation of an anionic alkoxo complex featuring a deprotonated methylene bridge, which is identified as the catalytically active species. Notably, the methylene linker exhibits previously unrecognized noninnocent behavior, undergoing reversible deprotonation and participating directly in proton-transfer steps of the catalytic cycle. Kinetic isotope effects and deuterium-labeling experiments support the involvement of both hydride transfer and alcohol-assisted proton processes in the rate-determining steps. These findings uncover a new mode of metal–ligand cooperation in triazolylidene-based manganese catalysts and provide mechanistic guidelines for the design of cooperative ligands in base-metal-borrowing hydrogen catalysis.2026info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://zaguan.unizar.es/record/171047reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/EC/H2020/101034288This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No H2020 101034288-IberusExperienceinfo:eu-repo/semantics/openAccessoai:dnet:zaguan______::acda99d7d6f095bf2126ca01131c7de82026-05-29T13:59:51Z
dc.title.none.fl_str_mv Methylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N-Alkylation
title Methylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N-Alkylation
spellingShingle Methylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N-Alkylation
Batuecas, Maria
title_short Methylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N-Alkylation
title_full Methylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N-Alkylation
title_fullStr Methylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N-Alkylation
title_full_unstemmed Methylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N-Alkylation
title_sort Methylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N-Alkylation
dc.creator.none.fl_str_mv Batuecas, Maria
Garcia, Beatriz
Saviozzi, Chiara
Viana, Maria S.
Maseras, Feliu
Royo, Beatriz
author Batuecas, Maria
author_facet Batuecas, Maria
Garcia, Beatriz
Saviozzi, Chiara
Viana, Maria S.
Maseras, Feliu
Royo, Beatriz
author_role author
author2 Garcia, Beatriz
Saviozzi, Chiara
Viana, Maria S.
Maseras, Feliu
Royo, Beatriz
author2_role author
author
author
author
author
description We elucidate the mechanism of the manganese-catalyzed N-alkylation of aniline with benzyl alcohol mediated by a bis(1,2,3-triazolylidene) Mn(I) complex through a combination of experimental studies and density functional theory (DFT) calculations. Activation of the precatalyst by a base leads to the formation of an anionic alkoxo complex featuring a deprotonated methylene bridge, which is identified as the catalytically active species. Notably, the methylene linker exhibits previously unrecognized noninnocent behavior, undergoing reversible deprotonation and participating directly in proton-transfer steps of the catalytic cycle. Kinetic isotope effects and deuterium-labeling experiments support the involvement of both hydride transfer and alcohol-assisted proton processes in the rate-determining steps. These findings uncover a new mode of metal–ligand cooperation in triazolylidene-based manganese catalysts and provide mechanistic guidelines for the design of cooperative ligands in base-metal-borrowing hydrogen catalysis.
publishDate 2026
dc.date.none.fl_str_mv 2026
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://zaguan.unizar.es/record/171047
url http://zaguan.unizar.es/record/171047
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/EC/H2020/101034288
This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No H2020 101034288-IberusExperience
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv
publisher.none.fl_str_mv
dc.source.none.fl_str_mv reponame:Zaguán. Repositorio Digital de la Universidad de Zaragoza
instname:Universidad de Zaragoza
instname_str Universidad de Zaragoza
reponame_str Zaguán. Repositorio Digital de la Universidad de Zaragoza
collection Zaguán. Repositorio Digital de la Universidad de Zaragoza
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869408825847578624
score 15,812429

Similares en LA Referencia